Electron transfer in Cobalt complexes using rigid ferrocenyl decorated polypyridyl based ligands

使用刚性二茂铁基修饰的聚吡啶基配体在钴配合物中进行电子转移

基本信息

批准号：
231408045
负责人：
Professor Dr. Heinrich Lang, since 5/2017
金额：
--
依托单位：
Professur Anorganische Chemie
依托单位国家：
德国
项目类别：
Research Grants
财政年份：
2013
资助国家：
德国
起止时间：
2012-12-31 至 2017-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/231408045?language=en
关键词：
Electron transfer Cobalt complexes using

项目摘要

Electron transfer processes are important steps in many chemical reactions. These processes proceed on very different time scales. Within this project hetero bimetallic complexes will be synthesized, after oxidation an intramolecular electron transfer will be found from a cobalt(II/III) ion to a ferrocenyl substituent. The employed hexadendate ligand around the cobalt ion is chosen that: on the one hand stable cobalt(II) complexes are formed, with high activation barrier for the oxidation to the cobalt(III) complex and on the other side the free reaction energy is low. Due to these properties the complex can be found in two metastable states that interconvert slowly.The large structural changes within the ligand sphere of the cobalt complexes stabilize the two states making them observable side by side at comparable high temperatures.Both states might be addressable by external stimuli like temperature change or light irradiation, making these molecules interesting for applications in data storage and molecular switches. Of high interest is the possible occurrence of an MMCT absorption (Metal to Metal Charges Transfer) accompanied with CTIST (Charge Transfer Induced Spin Transition) which allows inducing an electron transfer by irradiation of light.The electron transfer process will be studied in detail by means of electro chemical, nuclear and electron spin resonance spectroscopy as well as UV/Vis/NIR spectroscopy.

电子转移过程是许多化学反应的重要步骤。这些过程以非常不同的时间尺度进行。在该项目中，将合成异质双金属复合物，在氧化后，将发现分子内电子转移从钴（II/III）离子到甲基苯基取代基。选择了钴离子周围的六末期配体：一方面形成稳定的钴（II）配合物，具有高激活屏障，用于氧化钴（III）复合物，另一侧的自由反应能量很低。由于这些特性，可以在两个亚稳态的状态中找到复合物，这些状态可以缓慢互动。钴络合物的配体领域内的巨大结构变化稳定了这两个状态，使它们在可比的高温下可以并排观察到。由于温度变化或光辐射，使这些分子在这些分子中的应用，使这些分子在这些分子中都可以在数据中进行应用，从而使这些分子适用于数据存储，从而使这些分子在数据中变得有趣。感兴趣的是可能出现MMCT吸收（金属电荷转移到金属电荷转移）以及伴随CTIST（电荷转移诱导的自旋过渡），这允许通过光的光照射诱导电子传输。电子转移过程将通过电，核化学，核化学，核化学，核和电子旋转共振光谱以及UV/nir Spemospopy详细研究。